WO2007025606A1 - Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys and process for producing and use of the same - Google Patents

Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys and process for producing and use of the same Download PDF

Info

Publication number
WO2007025606A1
WO2007025606A1 PCT/EP2006/006928 EP2006006928W WO2007025606A1 WO 2007025606 A1 WO2007025606 A1 WO 2007025606A1 EP 2006006928 W EP2006006928 W EP 2006006928W WO 2007025606 A1 WO2007025606 A1 WO 2007025606A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
added
bath
polymer additive
general formula
Prior art date
Application number
PCT/EP2006/006928
Other languages
French (fr)
Inventor
Vaclav Kriz
Jiri Kloubek
Jiri Houfek
Original Assignee
Atotech Deutschland Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Publication of WO2007025606A1 publication Critical patent/WO2007025606A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/08—Polymerisation of formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C08G73/0226—Quaternisation of polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the invention relates to nitrogen polymer additives and a process for producing these additives as well as the use of them during electrolytic deposition of zinc and zinc alloys .
  • the advantages of the weakly acid chloride baths for zinc coating resides in deposition of highly decorative to brilliant coating, cathodic efficiency almost to 100 % and a very good covering power, that enables even a successful coating of members with a very complicated surface.
  • a disadvantage resides in the distribution of the thickness of the zinc coating in dependence on the local current density.
  • the shade after brightening and chromate treatment is deeper and less brilliant than that of the coating produced from weakly acid baths.
  • the rate of production of the coating is also relatively low due to the lower efficiency of the cathodic process .
  • the invention resides in the nitrogen polymer additive for electrolytic zinc and zinc alloy coating of formula I
  • a direct reaction of the monomers may be performed in an aqueous or in a suitable organic medium.
  • an appropriate amount of monomers of formulas I and II is firstly dissolved in a suitable solvent and then the halogen derivative is added step by step in such a manner as to avoid a too vigorous reaction.
  • the nitrogen monomers of formulas II and III are added in a molar ratio of 100:0 to 0 : 100.
  • For 1 mol of the mixture of the nitrogen monomers 0,5 to 1,5 mol, preferably 0,8 to 1,2 mol and most preferably 1 mol of the halogen derivative is used.
  • the range of possible reaction temperatures is 20 to 180, more preferably 80 to 120 0 C in dependency on the reaction components used.
  • the reaction can be well performed at the reflux temperature.
  • the typical reaction time is 1 to 48 hours and is dependent on the reaction components used.
  • the reaction conditions are selected to obtain a copolymer with alternating units of monomers described above with a molecular weight of the product of 300 to
  • the process for producing of the nitrogen polymer additive according to the invention allows changes of the charge density by selection of monomers and so an accurate optimalization of the features of the additive in dependency on the features of the bath and with respect to the final coating is possible.
  • the polymer produced is polycationic, therefore, for this reason in the electric field it is drawn to the cathode and there it intensively influences further cathodic processes, especially electroreduction of metals (Me x+ -xe ⁇ — Me) .
  • Nitrogen polymer additives thus produced are added to alkaline baths for zinc and zinc alloy plating that contain
  • the additives of formula I may be used individually or in combinations.
  • Metal Zn or ZnO that is dissolved chemically or electrochemically in a solution of alkali hydroxide or another soluble zinc compound may be used as a source of Zn.
  • the bath may also contain carbonate ions in an amount of not more than 100 g/1.
  • the nitrogen polymer additive according to the invention is added to the bath in an amount of 0,1 to 20 g/1 (of the active compound) .
  • complexes of Fe, Co, Ni or Mn may be added in an amount of 0,01 to 50 g/1. Further it is possible to add compounds that eliminate water hardness and metal impurities as silicates, polyhydroxy acids (tartrate, gluconate etc.) or other complexes forming compounds (EDTA) in an amount of 0,1 to 100 g/1. It is also possible to add further nitrogen oligomers or polymers for refining crystalline structure of the coating, e.g. reaction products of imidazole, morpholine or piperazine with epichlorhydrin and an aliphatic amine in an amount of 0,1 to 20 g/1.
  • Examples A - D (Use of the nitrogen polymer additive) :
  • the advantages of the baths prepared according to the present invention may be evaluated for example according to CSN 03 8530 (Electroplating in the Hull's bath).
  • Anode nickel coated steel anode current: IA for 15 minutes
  • Anode nickel coated steel anode current: IA for 15 minutes
  • Anode nickel coated steel anode current: IA for 15 minutes
  • Anode nickel coated steel anode current: IA for 40 minutes
  • the coating produced was subjected to a heat shock at a temperature of 10 0 C for 5 minutes. Then the coating was quickly cooled to room temperature and followed up for further 14 days. Production of blisters was not observed.
  • Anode nickel coated steel anode current: IA for 40 minutes
  • the coating produced was subjected to a temperature of 70 0 C for 14 days. It was not possible to observe any production of blisters.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The invention concerns a nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys as a reaction product of two amino derivatives with epichlorohydrin, dihalogenalkane or dihalogenelkylether. The invention describes also a process for producing this additive and its use.

Description

Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys and process for producing and use of the same
Field of the invention
The invention relates to nitrogen polymer additives and a process for producing these additives as well as the use of them during electrolytic deposition of zinc and zinc alloys .
Background of the invention
For ecological and hygienical reasons the use of toxic cyanide baths that during the 80th years of the 20th century occupied more than 50% of the whole capacity of the galvanic zinc coating is gradually abandoned. In the course of replacing these solutions two types of baths, i.e. weakly acid chloride baths and alkaline zincate baths are in competition.
The advantages of the weakly acid chloride baths for zinc coating resides in deposition of highly decorative to brilliant coating, cathodic efficiency almost to 100 % and a very good covering power, that enables even a successful coating of members with a very complicated surface. A disadvantage resides in the distribution of the thickness of the zinc coating in dependence on the local current density.
Alkaline baths for zinc coating suffered from the beginning from deficiencies that restricted their quicker introduction into industrial praxis. Among the greatest of them a restricted range of current densities allowing deposition of acceptable coatings may be mentioned. There has also been a tendency for blistering and a slow formation of the coating. Formation of coatings with an appearance comparable with that deposited from weakly acid baths has never been achieved.
From the beginning of the evolution of cyanide-free baths for zinc coating a great attention has been focused on the nitrogen polymers that often contained quaternary nitrogen. For example US Patent 3 824 158 protects reaction products of ,,aminated" polyepichlorohydrin with epichlorohydrin with respect to the quaternary character of the active compound. According to US Patent 3 853 718 polyalkyleneimme is modified with the aid of ammonium alkylhalogenide and US Patent 3 869 358 describes quartermzation of dimethylaminopropylamme with the aid of epichlorohydrin .
In further patent documents quaternary oligomers and polymers are synthetized with the aid of heterocyclic monomers . Of these monomers epichlorohydrin and aliphatic amine (US 3 974 045, US 4 397 717, US 4 730 022) or only epihalogenhydrin or glycerolhalogenhydrin (US 3 954 575 or US 4 045 306) can be named.
An important progress has been achieved by the use of polymers that contain N, N-bis [3- (dialkylammo) alkyl] urea as their basic monomer. For the synthesis of active compounds it is then possible to use polymeration with the use of various chlorinated dialkylethers (US 4 157 388, US 5 405 523, US 5 435 898) or dihalogenalkans (WO 00/014305) or with the use of dihalogenalkans and tertiary diamines (US 6 706 167) . The advantage of these processes resides particularly in the very good homogenity of the thickness of the layer that is produced from the zinc plating baths with the use of the polymers mentioned above. During the zinc plating it is, however, still not possible to attain sufficient gloss of the coating, the shade after brightening and chromate treatment is deeper and less brilliant than that of the coating produced from weakly acid baths. The rate of production of the coating is also relatively low due to the lower efficiency of the cathodic process .
All these disadvantages may be suppressed by the nitrogen polymer additive, a process for producing this additive and the use of this additive in alkaline baths for zinc and zinc alloy coating according to the present invention.
Summary of the invention
The invention resides in the nitrogen polymer additive for electrolytic zinc and zinc alloy coating of formula I
Figure imgf000004_0001
(I)
wherein Z means CH2-CH(OH)CH2 or (CrH2r) -0- (CrH2r) or CqH2q, wherein r = 1 to 6 and q =1 to 6, a = 0 to 1, b = 0 to 1, a + b = 1, x = 0 to 1, y = 0 to 1, x + y = 1 and n is at least 2, R, Ri, R',R'i independently mean CmH2m+i wherein m = 1 to 3 or -CH2OH or -CH2CH2OH or -CH2CH(OH)CH3 or -CH2CH(OH)CH2OH or may be identical, R2 means (CH2) c wherein c = 2 to 6,
R3 means C=O, C=S, C=NH or O=C (CH2) dC=0, wherein d =2 to 6, R'2 means (CH2) g, wherein g = 2 to 6 and
R' 3 means C=O, C=S, N=NH or O=C (CH2) hC=0, wherein h = 2 to 6, as a reaction product of at least one amino derivative of general formula II
Figure imgf000005_0001
(H)
and at least one amino derivative of general formula III
Figure imgf000006_0001
(III)
wherein all general symbols used have the meaning stated above, with at least one halogen derivative from the group of epihalogenhydrin and/or 1, 3-dichloro-2-hydroxypropan and/or dihalogenalkane of general formula X-(CqH2q)-X, wherein q=l to 6 and X means Cl, Br or I and/or dihalogenalkylether of general formula X- (CrH2r) 0- (CrH2r) -X wherein r = 1 to 6 and X means Cl, Br or I.
A direct reaction of the monomers may be performed in an aqueous or in a suitable organic medium. In the reactor an appropriate amount of monomers of formulas I and II is firstly dissolved in a suitable solvent and then the halogen derivative is added step by step in such a manner as to avoid a too vigorous reaction. The nitrogen monomers of formulas II and III are added in a molar ratio of 100:0 to 0 : 100. For 1 mol of the mixture of the nitrogen monomers 0,5 to 1,5 mol, preferably 0,8 to 1,2 mol and most preferably 1 mol of the halogen derivative is used. The range of possible reaction temperatures is 20 to 180, more preferably 80 to 1200C in dependency on the reaction components used. The reaction can be well performed at the reflux temperature. The typical reaction time is 1 to 48 hours and is dependent on the reaction components used. The reaction conditions are selected to obtain a copolymer with alternating units of monomers described above with a molecular weight of the product of 300 to
1 000 000, preferably 1000 to 10 000. Positively charged quaternary nitrogen atoms are regularly repeated in the final chain. The process for producing of the nitrogen polymer additive according to the invention allows changes of the charge density by selection of monomers and so an accurate optimalization of the features of the additive in dependency on the features of the bath and with respect to the final coating is possible. The polymer produced is polycationic, therefore, for this reason in the electric field it is drawn to the cathode and there it intensively influences further cathodic processes, especially electroreduction of metals (Mex+-xe~— Me) .
Nitrogen polymer additives thus produced are added to alkaline baths for zinc and zinc alloy plating that contain
2 to 50 g/1, more preferably 8 to 15 g/1 of Zn and further 10 to 300, preferably 90 to 160 g/1 of NaOH and/or KOH and/or LiOH, the additives of formula I may be used individually or in combinations. Metal Zn or ZnO that is dissolved chemically or electrochemically in a solution of alkali hydroxide or another soluble zinc compound may be used as a source of Zn. The bath may also contain carbonate ions in an amount of not more than 100 g/1. The nitrogen polymer additive according to the invention is added to the bath in an amount of 0,1 to 20 g/1 (of the active compound) . For deposition of zinc alloys complexes of Fe, Co, Ni or Mn may be added in an amount of 0,01 to 50 g/1. Further it is possible to add compounds that eliminate water hardness and metal impurities as silicates, polyhydroxy acids (tartrate, gluconate etc.) or other complexes forming compounds (EDTA) in an amount of 0,1 to 100 g/1. It is also possible to add further nitrogen oligomers or polymers for refining crystalline structure of the coating, e.g. reaction products of imidazole, morpholine or piperazine with epichlorhydrin and an aliphatic amine in an amount of 0,1 to 20 g/1. The gloss in the range of low current densities may be ameliorated by compounds containing divalent sulphur as Na2S, thiourea and its derivatives or heterocyclic compounds containing the group C=S (as imidazoline thion) . These compounds are added to a concentration of 0,01 to 5 g/1. Gloss, levelling and brilliancy may be influenced by aromatic aldehydes (vanillin, heliotropin, anisaldehyde) and further aromatic compounds (benzylpyridinium-3-carboxylate) , in an effective concentration of 0,001 to 1 g/1. Electroplating is performed at a temperature of 10 to 60, preferably 20 to 300C, with the use of steel anodes, zinc anodes or nickel coated steel anodes.
From such baths it is possible to plate zinc or zinc alloy coatings with a number of advantageous features. The coatings produced for example have fully homogenous thickness also on very complicated parts, a high brilliant gloss, comparable with that plated from weakly acid baths and sufficient drawability without tendency to produce blisters. At the same time the baths retain their current efficiency that in the industrial praxis enables a more effective work than with the use of known technologies. The invention will now be illustrated by working examples that are not intended for restricting the scope of the invention. Examples 1 to 4 (process for producing the nitrogen polymer additive)
Example 1
32,6 g (0,2 mol) of N- (3-dimethylaminoethyl) urea and 4,3 g (0,02 mol) of N, N ' -bis (3-dimethylaminoethyl) urea was dissolved in a mixture of 20 ml of water and 10 ml of ethanol, to this solution 24,8 g (0,22 mol) of 1,3- dichloropropane was added and the reaction mixture was refluxed 6 hours, then diluted by 30 ml of water and the reaction product was filtered off with the aid of charcoal. 120 g of a water solution of the polymer with a concentration of about 50 % was obtained.
Example 2
0,41 g (0,002 mol) of N- (3-diethylaminobutyl) thiourea, 2,6 g (0,018 mol) of N- (3-dimethylaminopropyl) urea and 56,5 g (0,18 mol) N, N ' -bis (3-dipropylaminopentyl) urea was dissolved in 100 ml of THF and to this solution 18,5 g (0,2 mol) of epichlorhydrin was added and the whole mixture was refluxed 12 hours. Then THF was distilled off under reduced pressure, 40 ml of water was added and the mixture was filtered with the aid of charcoal. 100 g of a water solution of the polymer with a concentration of about 60 % was obtained.
Example 3
29 g (0,2 mol) of N- (3-dimethylaminopropyl) urea, 5,9 g (0,02 mol of N, N ' -bis (3-dimethylaminopropyl) thiourea and 39 g (0,18 mol of N, N' -bis (3-dimethylaminoethyl) urea was dissolved in 100 ml of water and to this solution 57,2 g (0,4 mol) of dichloroethylether was added and the reaction mixture was refluxed 24 hours. Then 200 ml of water was added and the mixture was filtered with the aid of charcoal .
4000 g of a water solution of the polymer with a concentration of about 30 % was obtained.
Example 4
26 g (0,18 mol) of N- (3-dimethylaminopropyl) urea, 3,22 g (0,02 mol) of N- (3-dimethylaminopropyl) thiourea and 46 f (0,02 mol) N, N'-bis (3-dimethylaminopropyl) urea was dissolved in a mixture of 20 ml of water and 80 ml of ethanol. To this solution 56,4 g (0,4 mol) of 1,5- dichloropentane was added and the reaction mixture was refluxed 16 hours, diluted by 330 ml of water and the reaction product was filtered off with the aid of charcoal. 530 g of a water solution of the polymer with a concentration of about 30 % was obtained. Examples A - D (Use of the nitrogen polymer additive) : The advantages of the baths prepared according to the present invention may be evaluated for example according to CSN 03 8530 (Electroplating in the Hull's bath).
Example A
Basic zinc-plating solution: 12 g/1 Zn 120 g/1 NaOH 20 g/1 Na2CO3
Anode: nickel coated steel anode current: IA for 15 minutes
1,5 g of the polymer of Example 1
20 mg/1 BNC
20 mg/1 vanillin
after brightening in 0,5% nitric acid for 5 seconds a brilliant coating has been obtained without fog with a brilliancy comparable with that produced from weakly acid baths. The thickness of the coating was 2,5 cm from the higher current densities (point B) and 2,5 cm from the low current desities (point A). B/A 1,2 B+A 15,5.
Example B
Basic zinc-plating solution: 12 g/1 Zn 120 g/1 KOH 20 g/1 K2CO3
Anode: nickel coated steel anode current: IA for 15 minutes
0,5 g of the polymer of Example 2
50 mg/1 BNC
20 mg/1 vanillin
after brightening in 0,5% nitric acid for 5 seconds a brilliant coating has been obtained without fog with a brilliancy comparable with that produced from weakly acid baths. The thickness of the coating was 2,5 cm from the higher current densities (point B) and 2,5 cm from the low current desities (point A). B/A 1,15 B+A 15,8. Example C
Basic zinc-plating solution: 12 g/1 Zn 120 g/1 NaOH 20 g/1 Na2CO3
Anode: nickel coated steel anode current: IA for 15 minutes
1,5 g of the polymer of Example 3
50 mg/1 benzylpyridinium-3-carboxylate
20 mg/1 vanillin
after brightening in 0,5% nitric acid for 5 seconds a brilliant coating has been obtained without fog with a brilliancy comparable with that produced from weakly acid baths. The thickness of the coating was 2,5 cm from the higher current densities (point B) and 2,5 cm from the low current desities (point A). B/A 1,25 B+A 15,4.
Example D
Basic zinc-plating solution:
12 g/1 Zn
120 g/1 NaOH
20 g/1 Na2CO3
50 mg/1 Fe
30 g/1 natrium gluconate
Anode: nickel coated steel anode current: IA for 15 minutes 1,5 g of the polymer of Example 4
50 mg/1 BNC
20 mg/1 vanillin
after brightening in 0,5% nitric acid for 5 seconds a brilliant coating has been obtained without fog with a brilliancy comparable with that produced from weakly acid baths.
Test for adhesion of the coating: a)
Basic zinc-plating solution:
12 g/1 Zn
120 g/1 NaOH
20 g/1 Na2CO3
Anode: nickel coated steel anode current: IA for 40 minutes
1,5 g of the polymer of Example 1
50 mg/1 benzylpyridinium-3-carboxylate
20 mg/1 vanillin
the coating produced was subjected to a heat shock at a temperature of 10 0C for 5 minutes. Then the coating was quickly cooled to room temperature and followed up for further 14 days. Production of blisters was not observed.
b)
Basic zinc-plating solution:
12 g/1 Zn
120 g/1 NaOH 20 g/1 Na2CO3
Anode: nickel coated steel anode current: IA for 40 minutes
0,5 g of the polymer of Example 2
50 mg/1 benzylpyridinium-3-carboxylate
20 mg/1 vanillin
the coating produced was subjected to a temperature of 700C for 14 days. It was not possible to observe any production of blisters.

Claims

C l a i m s
1. Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys of general formula I
Figure imgf000015_0001
(I)
wherein
Z means CH2-CH(OH)CH2 or (CrH2r) -0- (CrH2r) or CqH2q, wherein r = 1 to 6 and q =1 to 6, a = 0 to 1, b = 0 to 1, a + b = 1, x = 0 to 1, y = 0 to 1, x + y = 1 and n is at least 2, R, R1, R',R'i independently mean CmH2m+i wherein m = 1 to 3 or -CH2OH or -CH2CH2OH or -CH2CH(OH)CH3 or -CH2CH(OH)CH2OH or may be identical, R2 means (CH2) c wherein c = 2 to 6,
R3 means C=O, C=S, C=NH or O=C (CH2) dC=0, wherein d =2 to 6, R' 2 means (CH2J9, wherein g = 2 to 6 and
R' 3 means C=O, C=S, N=NH or O=C (CH2) hC=0, wherein h = 2 to 6, as a reaction product of at least one amino derivative of general formula II
Figure imgf000016_0001
(H) and at least one amino derivative of general formula III
Figure imgf000016_0002
wherein all general symbols used have the meaning stated above, with at least one halogen derivative from the group of epihalogenhydrin and/or 1, 3-dichloro-2-hydroxypropan and/or dihalogenalkane of the general formula X- (CqH2q) -X, wherein q=l to 6 and X means Cl, Br or I and/or dihalogenalkylether of the general formula X- (CrH2r) 0- (CrH2r) -X wherein r = 1 to
6 and
X means Cl, Br or I.
2. A process for producing a nitrogen polymer additive of claim 1, c h a r a c t e r i z e d i n t h a t 1 mol of a mixture of amino derivatives is contacted with 0,5 to 1,5 mol of a halogen derivative in an aqueous or in a suitable organic medium at a temperature of 200C to the reflux temperature, preferably 900C to the reflux temperature for 1 to 48 hours.
3. Use of the nitrogen polymer additive according to claim 1 for electrolytic deposition of zinc and zinc alloys wherein 0,1 to 20 g/1 of the nitrogen polymer additive is added to a zinc plating bath containing 2 to 50 g/1 of Zn, 10 to 300 g/1 of NaOH and/or KOH and/or LiOH and optionally to 100 g/1 Na2CO3.
4. The use according to claim 3, wherein complex Fe and/or Co and/or Ni and/or Mn is added to the bath in an amount of 0,01 to 50 g/1.
5. The use according to claims 3 and 4 wherein selected nitrogen oligomers or polymers are added to the bath in an amount of 0,1 to 20 g/1.
6. The use according to any of the claims 3 to 5, wherein compounds containing divalent sulphur, Na2S and/or thiourea and its derivatives and/or heterocyclic compounds containing the group C=S are added to the bath in an amount of 0,01 to 5 g/1.
7. The use according to any of the claims 3 to 6, wherein aromatic aldehydes and/or other aromatic compounds are added to the bath in an amount of 0,001 to 1 g/1.
8. The use according to any of the claims 3 to 7, wherein silicates, polyhydroxy acids or other compounds forming complexes are added to the bath in an amount of 0,1 to
100 g/1.
PCT/EP2006/006928 2005-07-14 2006-07-14 Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys and process for producing and use of the same WO2007025606A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ20050456A CZ2005456A3 (en) 2005-07-14 2005-07-14 Nitrogenous polymeric ingredient for electrolytic deposition of zinc and zinc alloys, process for its preparation and use thereof
CZPV2005-456 2005-07-14

Publications (1)

Publication Number Publication Date
WO2007025606A1 true WO2007025606A1 (en) 2007-03-08

Family

ID=36942248

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/006928 WO2007025606A1 (en) 2005-07-14 2006-07-14 Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys and process for producing and use of the same

Country Status (2)

Country Link
CZ (1) CZ2005456A3 (en)
WO (1) WO2007025606A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2292679A1 (en) * 2009-09-08 2011-03-09 ATOTECH Deutschland GmbH Polymers with amino end groups and their use as additives for galvanic zinc and zinc alloy baths
US20120138473A1 (en) * 2010-09-09 2012-06-07 Yuken Industry Co., Ltd. Zinc plating bath additive and alkaline non-cyanide zinc plating bath
DE102011116764A1 (en) 2011-10-22 2013-04-25 Gonzalo Urrutia Desmaison New cationic polymer comprising polycationic section and uncharged water-soluble section obtained by polycondensing amine or heteroaryl with epihalohydrin in water and reacting with polyol, useful e.g. as additives in galvanic copper baths
CN103510133A (en) * 2013-07-09 2014-01-15 韶关美妥维志化工有限公司 Carrier brightening agent as well as preparation method and application thereof
CN103952733A (en) * 2013-12-23 2014-07-30 韶关美妥维志化工有限公司 Carrier brightener precursor and carrier brightener for alkaline zinc-plating or zinc alloy electroplating solution and electroplating solution
US9439294B2 (en) 2014-04-16 2016-09-06 Rohm And Haas Electronic Materials Llc Reaction products of heterocyclic nitrogen compounds polyepoxides and polyhalogens
US20200071843A1 (en) * 2016-05-24 2020-03-05 Coventya, Inc. Ternary zinc-nickel-iron alloys and alkaline electrolytes or plating such alloys
EP3933073A1 (en) * 2020-06-29 2022-01-05 ATOTECH Deutschland GmbH Copper electroplating bath

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5405523A (en) * 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
US5435898A (en) * 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes
US6652728B1 (en) * 1998-09-02 2003-11-25 Atotech Deutschland Gmbh Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5405523A (en) * 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
US5435898A (en) * 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes
US6652728B1 (en) * 1998-09-02 2003-11-25 Atotech Deutschland Gmbh Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013503968A (en) * 2009-09-08 2013-02-04 アトテック・ドイチュラント・ゲーエムベーハー Polymers having terminal amino groups and their use as additives for zinc or zinc alloy electrodeposition baths
WO2011029781A1 (en) 2009-09-08 2011-03-17 Atotech Deutschland Gmbh Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths
KR101763756B1 (en) 2009-09-08 2017-08-01 아토테크더치랜드게엠베하 Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths
US9322107B2 (en) 2009-09-08 2016-04-26 Atotech Deutschland Gmbh Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths
EP2292679A1 (en) * 2009-09-08 2011-03-09 ATOTECH Deutschland GmbH Polymers with amino end groups and their use as additives for galvanic zinc and zinc alloy baths
EP2489762A4 (en) * 2010-09-09 2012-12-05 Yuken Kogyo Co Ltd Additive for zinc plating baths and non-cyanide alkaline zinc plating baths
EP2489762A1 (en) * 2010-09-09 2012-08-22 Yuken Industry Co., Ltd. Additive for zinc plating baths and non-cyanide alkaline zinc plating baths
US20120138473A1 (en) * 2010-09-09 2012-06-07 Yuken Industry Co., Ltd. Zinc plating bath additive and alkaline non-cyanide zinc plating bath
DE102011116764A1 (en) 2011-10-22 2013-04-25 Gonzalo Urrutia Desmaison New cationic polymer comprising polycationic section and uncharged water-soluble section obtained by polycondensing amine or heteroaryl with epihalohydrin in water and reacting with polyol, useful e.g. as additives in galvanic copper baths
CN103510133A (en) * 2013-07-09 2014-01-15 韶关美妥维志化工有限公司 Carrier brightening agent as well as preparation method and application thereof
CN103510133B (en) * 2013-07-09 2016-04-06 韶关美妥维志化工有限公司 A kind of carrier brightening agent and its preparation method and application
CN103952733A (en) * 2013-12-23 2014-07-30 韶关美妥维志化工有限公司 Carrier brightener precursor and carrier brightener for alkaline zinc-plating or zinc alloy electroplating solution and electroplating solution
US9439294B2 (en) 2014-04-16 2016-09-06 Rohm And Haas Electronic Materials Llc Reaction products of heterocyclic nitrogen compounds polyepoxides and polyhalogens
US10190226B2 (en) 2014-04-16 2019-01-29 Rohm And Haas Electronic Materials Llc Reaction products of heterocyclic nitrogen compounds polyepoxides and polyhalogens
US20200071843A1 (en) * 2016-05-24 2020-03-05 Coventya, Inc. Ternary zinc-nickel-iron alloys and alkaline electrolytes or plating such alloys
US11913131B2 (en) * 2016-05-24 2024-02-27 Macdermid, Incorporated Ternary zinc-nickel-iron alloys and alkaline electrolytes or plating such alloys
EP3933073A1 (en) * 2020-06-29 2022-01-05 ATOTECH Deutschland GmbH Copper electroplating bath
WO2022002899A1 (en) * 2020-06-29 2022-01-06 Atotech Deutschland Gmbh Copper electroplating bath

Also Published As

Publication number Publication date
CZ2005456A3 (en) 2007-01-31

Similar Documents

Publication Publication Date Title
WO2007025606A1 (en) Nitrogen polymer additive for electrolytic deposition of zinc and zinc alloys and process for producing and use of the same
US20100155257A1 (en) Aqueous, alkaline, cyanide-free bath for the galvanic deposition of zinc alloy coatings
EP2111484B1 (en) Polyamine brightening agent
GB2294472A (en) Cationic quaternary ammonium polymer additive in alkaline zinc and zinc alloy electroplating baths
AU764300B2 (en) Zinc and zinc alloy electroplating additives and electroplating methods
EP2350355B1 (en) Zinc alloy electroplating baths and processes
EP1639155B1 (en) Zinc and zinc-alloy electroplating
EP1315849B1 (en) Zinc and zinc alloy electroplating methods
US20110210007A1 (en) Zincate zinc plating bath
US6387229B1 (en) Alloy plating
JP5853283B2 (en) Zinc-nickel alloy plating solution and plating method
JP5747359B2 (en) Zincate-type zinc-based plating bath, additive for zincate-type zinc-based plating bath, and method for producing zinc-based plated member
JP4855631B2 (en) Zinc and zinc alloy electroplating additive and electroplating method
JP2997072B2 (en) Zinc-nickel alloy plating bath and method for preventing black deposition on plating object
WO2022186183A1 (en) Additive for acidic zinc alloy plating bath, acidic zinc alloy plating bath and zinc alloy plating film
JPS6319600B2 (en)
JP2014037621A (en) Zincate type galvanizing bath, additive for zincate type galvanizing bath and method for producing galvanized member
US20230015534A1 (en) Electroplating composition and method for depositing a chromium coating on a substrate
RU2206641C1 (en) Bright zinc plating electrolyte
CZ2004855A3 (en) Nitrogenous polymeric additive for electrolytic deposition of zinc, process for its preparation and use thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06818230

Country of ref document: EP

Kind code of ref document: A1